Iii iv

ABSTRACT

VAT DYEING POLYHDROXYLATED TEXTILE MATERIALS SUCH AS CELLULOSIC OR POLYVINYL ALCOHOL FIBROUS MATERIALS WITH VAT DYES HAVING TWO ANTHRAQUINONE GROUPS OR 5 FUSED RINGS, EACH OF SAID DYES HAVING A SULFONATED BENZOYLAMINO GROUP THEREON. IN AN EXAMPLE, THE VAT DYE IS   1-NH2,2-((=N-(ANTHRAQUINON-2,3-YLENE)-S-)&gt;C-),3-((4-(NA-   O-SO2-)PHENYL)-CO-NH-)ANTHRAQUINONE

United States Patent Ofiice Re. 27,470 Reissued Sept. 5, 1972 Matterenclosed in heavy brackets appears in the original patent but forms nopart of this reissue specification; matter printed in italics indicatesthe additions made by reissue. v

ABSTRACT OF DISCLOSURE Vat dyeing polyhydroxylated textile materialssuch as cellulosic or polyvinyl alcohol fibrous materials with vat dyeshaving two anthraquinone groups or fused rings, each of said dyeshavinga sulfonate'd benzoylamino group thereon. In, an example, the vat dye ise C/N i 5 @Q- \m This is a continuation in part of our application Ser.No. 155,479 filed Nov. 28, 1961, now abandoned.

It is known that vattable polycyclic quinones containing at least onehydrophylic group and at least one group that is capable of being fixedby chemical means, yield valuable and fast dyings on polyhydroxylatedmaterials such as textiles of polyvinyl alcohol or especially ofcellulose, when at least one stage of the process is carried out in thepresence of a reducing agent.

The present invention is based on the surprising observation thatequally fast dyings can be obtained in accordance with the aboveprocedure by using a vattable, polycyclic quinone despite the, fact thatit contains no group that can combine chemically with thepolyhydroxylated material. The present invention thus concerns a processfor coloring polyhydroxylated fibrous materials with vattable,polycyclic quinones, wherein in at least one stage of the process apolycyclic quinone is reduced to its leuco forrrr in the presence of analkaline reducing agent and wherein the polycyclic, vattable quinonewhich is subsequently reoxidized on'the fibers is free from reactivegroup and from azo linkage but contains at least one acylamino groupbound by its-CO-NH-group and at least one sulfonic acid group bond tothe chromophore through its sulfur atom and is selected from thosehaving at least 5 condensed rings and those having at least 2anthraquinone residues.

Polycyclic quinones of the above-mentioned type are those which onreduction yield the so-called leuco form.

or vat, whichlatter form has a higher degree of afiinity for natural orregenerated cellulose fibers thanhas the unreduced form, and which canbe reoxidizedIto the original chromophore system. Especially suitablequinones are those of the anthraquinone series, for example, thosecontaining a 9:10-dioxoanthracene ring condensed on to at least twocarboxylic or heterocyclic rings, or that comprise two to threeanthroquinoue residues, for example, two such residues bound togetherdirectly, that is to say by a direct bond, or by a double bond orthrough an organic bivalent bridge. Such bivalent bridges are, forexample, the --NH- and CH=NN=CH- groups, thealkylene-arylene-diarnineand dior polycarboxylic acid radicals,hetcrocyclic rings such as one or more imidazole-, triazole-, triazine-,cyameluric acid-, pyridine-, quinazoline, oxazole-, or thiazole rings.Two anthraquinone residues which may be similar to or diifer from oneanother, may be bound together across such a bridge system. The vattablepolycyclic quinones used in the process of the invention are thus vatdyestuffsulfonic acids whose sulfonic acid group is not hydrolysed inthe vat. After the reoxidation, the wt dyestuffsulfonic acid isregenerated on the dyed fiber. The above polycyclic quinones thereforeclearly distinguished from the dyestuffs described in US. Patent No.2,778,839 to Peter which are no vat dyestuffs and from the dyestufi' ofUS. Patent No. 3,110,541 to Weber whose sulfonic acid groups areeliminated in the vat together with the acyl residues to which they arebound. They are also distinct from the wool dyes of US. Patent No.2,093,355, which are not vat dyestulfs, as well as from the reactivedyes such as those of U.S. Patents No. 3,031,252 and No, 2,895,785.

The vattable polycyclic quinone to be used in the process of theinvention are preferably free from azo linkages and belong to the vatdyestuff class of the anthraquinone series. They may contain one of thefollowing polycyclic quinone residues: 'I'hiophanthraquinone,anthrapyrimidine, anthrapyridone, isothiazoleanthrone,quinazolineanthraquinone, oxazoleanthraquinone, thiazoleanthraquinone,anthraquinonyltriazole, acylaminoanthraquinone, pyrazoleanthraquinone,dipyrazoleathronyl, pyrazinoanthraquinone, anthraquinone-hydrazone,azomethinc-anthraquinone, azaanthraquinone, azabenzanthrone,anthraquinoneacridone, indanthrone, thioxanthoneanthraquinone,anthrirnide, di-, trior tetraanthrimide-carbazole, dihydroacridine,anthanthrone, pyranthrone, dibenzyrenquinone, dibenzanthrone,isodibenzanthrone, flavanthrone, acedianthrone and phthaloyl compoundsof bior poly-nuclear hydrocarbons. One or two acylamino, preferablyaroyl amino groups must be bound to the quinone by their CONH-groupingsand there must be present one to three stable sulfonic acid groups i.e.groups bound by their sulfur atom to the chromophore, so that they arenot eliminated in the vat. The sodium salts of the vat dyestuff-sulfonicacids used in the process of the invention have a water solubility of atleast 5 grams per liter, preferably 10 to 100 grams per liter, at C.

The polycyclic quinones used in the process are obtained by sulfonating,or using chlorosufonic acid to chlorosulfonate, the above-mentionedpolycyclic quinones which contain at least 5 condensed rings or at least2 anthraquinone residues, or by treating the corresponding quinoneswhich contain at least one acylatable NH group, with an acylating agent,especially with an aromatic carboxylic acid-halide, which contains atleast one SO H or one halogen -SO group.

The dyestuffs obtained in the above manner may be used for padding,dyeing in a dye bath of printing cellulose-containing materialsincluding those of artificial fibers, for example, regenerated celluloseor viscose materials, or natural products such as linen or above allcotton. For these processes, the particular dyestufi may suitably beused as an aqueous solution or suspension there- )f or as an ingredientin a printing paste. Cotton may be lyed with the dyestuif by the knownPadroll Process, vherein the padded material is wound on a spool which sslowly rotated while dyeing at the desired temperature.

The dyeing is usually advantageously carried out at I. temperature belowthat which is normally used in the :otton dyeing industry, for example,at a temperature :elow 90 C., for example, at about 50 C. In orderfacilitate the exhaustion of the dye bath, it is advisable 0 add a moreor less neutral and above all an inorganic ialt such as an alkali-metalchloride or alkali-metal sul- ?ate, if desired portionwise, to the dyebath, either together with the dyestufl or during the course of thedyeng process. Advantageously, the dye bath is adjusted to L distinctlyalkaline pH-value, either during or at the tart of the process, byadding an alkali, for example,

odium carbonate or potassium carbonate, or above all 1y adding asolution of an alkali-metal hydroxide.

The reducing agent used may be a strong reducing igent such as sodiumhydrosulfite, thiourea dioxide, or, f desired, it may be a weak reducingagent such as odium sulfide, sodium hydrosulfide or glucose. TheLl'l'lOllIlt of reducing agent used may vary within wide imits. In manycases, a substantially smaller amount of educing agent need be used thanis usually-required vhen vat or sulfur dyestuifs are used.

The reducing agent may be introduced at the begining, luring the courseor towards the end of the dyeing )rocess.

Instead of preparing a dye bath (by adding the vattable ompound, thereducing agent and, if desired, the more r less neutral inorganic salt,together or consecutively 0 water), the dyestuff and the salts may,alternatively, e made up into a stiif paste or preferably into a dryireparation.

By the present process, polyhydroxylated materials, specially cellulosetextiles are provided with dyeings or -rints that have excellent wetfastness properties and very :ood fastness to light.

In contradistinction to known vat dyeing processes, he process of thepresent invention is much simpler wing to the fact that the preliminaryvatting procedure a the stock vat can either be omitted entirely or atany ate can be substantially accelerated and simplified. Furhermore, theprocess is not so dependent vupon the temerature used. The presentinvention provides dyeings which have a high degree of uniformity andpenetration. "ull and very even dyeings are obtained, especially onegenerated cellulose, and the tints provided by correponding dyeings areoften the same on regenerated cellu- Jse as on cotton.

The following examples illustrate the invention. Un'-- :ss otherwiseindicated the parts and percentages are 'arts and percentages by weight,and the relationship etween parts by weight and parts by volume is thesame s that between the kilogram and the liter:

EXAMPLE 1 0.15 part of the dyestuft of the formula 0 (H) NH} /N NH-OO-OSmONa hich is obtained by condensing the corresponding aminechloride. The cotton is then squeezed out, oxidized in in the air,rinsed, acidified, rinsed again and fiinally soaped at the boil. Thegreenish blue dyeing so obtained has very good properties of fastness tolight and wetness.

EXAMPLE 2 In the manner described in Example 1, there is used 0.15 partof the dyestuif of the formula I .1;

SOzONB which has a solubility in water of 15 grams per liter at C. andwhich is obtained by condensing the sulfochloride of 2 phenyl 4,6dichloro triazine- (1 3 :5) with 2 molecular proportions ofl-amino-anthraquinone in nitrobenze'ne, at 140 C., and hydrolysing theSO CI by vatting and reoxidizing. A yellow dyeing 'of excellent fastnessisobtained.

EXAMPLE 3 In the manner described in Example I there is used 0.15 partof the dyestuff of the formula V SOzONB --O o -GH: CHI-O O which has awater solubility of 20 grams per liter at 95 n C. and which is obtainedby condensing the sulfochloride of 2-phenyl-4z6-dichloro-113:5-triazinewith zfmolecular proportions of 1:4 diamino-Z-acetyI-anthraquinOne'innitrobenzene at C vatting the sulfochloride and 're-.

oxidizing the dyestufi. A blue dyeing of excellent fastness is obtained.

EXAMPLE 4 0.2 part of the dyestuff of the formula which has a solubilityin water of 12 grams per liter at 95 C. is used in the manner describedin Example 1. A golden orange dyeing of excellent fastness is obtained.The above dyestuif is obtained in the following manner:

24.2 parts of benzoic acid-para-sulfochloride in 250 parts ofnitrobenzene are heated, at 100-110" C. for 1 hour and with stirring,with 20 parts of thionyl chloride and 0.5 part of dimethyl formamide. Aclear solution is obtained from which the exces thionyl chloride isremoved by distillation under reduced pressure. 22.9 parts of5:5-diamino-1:l-dianthrimidecarbazole are then added and the mixture iskept at 120-125 C. for 21 hours. After cooling, the crystallizeddyestufi is filtered, washed with benzene, vatted reoxidized, filteredand dried.

B using the same amount of benzoic acid-metasulfochloride instead of thebenzoic acid-para-sulfochloride, or an equivalent amount of para-benzoicacid-sulfofluoride, similar dyestulfs with similarly excellentproperties of fastness are obtained.

EXAMPLE 5 015 part of the dyestuff of the formula is used in the mannerdescribed in Example .1. A full brown dyeing of good properties offastness is obtained.

The dyestuif may be obtained in the following manner:'

24.2 parts of benzoic 'acid-par-sulfochloride in 250 parts ofnitrobenzene are heated at 100-110i C. for 1 hour, with 20 parts ofthionyl chloride and 0.5 part of dimethyl forrnamide. The excess thionylchloride is then distilled oli under reduced pressure. 21.8 partsof'diamino acedianthrone are then added at 100 C. and the mixture isheated at 120125 C., with stirring, for 8 hours. After cooling, thecrystallized dyestuif is filtered, washed with nitro'benzene andbenzene, vattcd in order to hydrolize the --SO- C1 group, reoxidized andthen dried.

By using the same amount of benzoic acid-metasulfochloride instead ofthe beuzoic acid-para-sulfochlor'ide a very similar dyestulf withsimilarly excellent properties of fastness is obtained.

EXAMPLE 6 fabric is then developed or vatted for 30 minutesin a bath, at50 0, containing per 1000 part s of water, 20

parts by-volume of a sodium hydroxide solution of 30% strength and 18parts of sodium hydrosulfite. After this ONa dyeing process the dyedmaterial is oxidized, rinsed, acidified, rinsed again and then soaped atthe boil. A greenish blue dyeing of excellent fastness is obtained.

By using 9 parts of thiourea dioxide instead of the 18 parts of sodiumhydrosulfite, similarly good results are obtained.

The above-mentioned dyestutf solution in the following manner:

14 parts of the dyestuff used in Example 1 are finely milled with 14parts of sodium dinaphthyl-methane-disulfonate and 112 parts of water ina ball mill. 100 parts of the 10% dyestuif paste so obtained are thendiluted with 900 parts of water. 5

may be prepared EXAMPLE 7 f Pad-jig process 14 parts of-the dyestuffused in Example 4 are finely,

EXAMPLE 8 Pad-steam process 100 parts of the 10% dyestufi' pastedescribed in Ex-J- ample 6 are diluted with 900 parts of water. Theresulting;

solution is used to impregnate cottoin fabric until amoisturenptake ofhas been reached. I

The fabric, which may or may not first be dried, is

then re-impregnated with a solution containing per 1000 parts of water,25 parts of sodium hydroxide solution of 30% strength and 20 parts ofsodium hydrosulfite. The squeezing-effect amounts to 80-120%. It is thensteamed for 30-60 seconds and finally after-treated in the mannerdescribed in Example 1. A blue dyeing of excellent fastness to light andwashing is obtained.

EXAMPlJE 9 v dyestutf paste used in-Example-7 ,-in

By using the 10% the process described in Example 8, similarly. goodresults are obtained.

EXAMPLE 10;

Wet-padding steam process to 30 C., 30parts by volume of a sodiumhydroxidesolw tion of 30% strength and 20 parts of sodium hydrosultiteare added to the solution obtained, which is then diluted with water toa total of 1000 parts.

. Cotton fabric is padded with the above solution and then immediatelysteamed in a steam vessel for 30-60 seconds. The fabric is then' rinsed,oxidized and soaped at :he boil in the manner described in Example 6. Ablue iyeing of outstanding fastness to light and washing is abtained.

Similarly good results are obtained by using a mixture )f 40 parts ofsodium sulfide and 10 parts of sodium iydrosulfite instead of the 20parts of sodium hydrosulfite.

EXAMPLE 11 The 10% dyestutr' paste used in Example 7 may be lsed insteadof the dyestufi in the process described in Example 10 to yield a yellowdyeing which is similarly Fast to washing at the boil.

EXAMPLE 12 Single-bath steam process Cotton fabric is padded at 30 C.with a solution conaining per 1000 parts of water, 100 parts of the 10%lyestutr' paste described in Example 6, 50 parts of urea, i parts ofpotassium hydroxide and 70 parts of sodium :ormaldesulfoxylate. It isthen dried at 60-80 0., steamed For minutes and the dyeing is thenafter-treated by oxilizing, soaping etc., in the manner described inExample 5. A greenish blue dyeing of outstanding general proper- ;ies offastness is obtained.

EXAMPLE 13 By using the dyestufi' paste of Example 7 in the mannerdescribed in Example 12, a yellow dyeing that s fast to washing at theboil and to light is obtained.

By applying the above-mentioned dyestuff to linen 'abric, similarly gooddyeings are obtained.

EXAMPLE 14 Molten-metal process 400 parts of the 10% dyestuif paste usedin Example 6 ire diluted with 900 parts of water. The solution obtaineds used to impregnate cotton fabric until a bath uptake of '0% has beenachieved. I

The so-padded fabric, with or without an intermediary lrying, is passedthrough a solution containing per 1000 salts of water, 22 parts byvolume of a sodium hydroxide olution of 30% strength and 18 parts ofsodium hydrom'lfite. I Y Y The fabric is then processed by passing itthrough ath containing an alloy of low melting point immediately ifterleaving the chemical bath. The fabric is retained in he metal bath, at90 C., for 5-15 seconds.-

After leaving the metal bath, the fabric is rinsed, oxilized,rinsedagain and finally soaped at the boil. A greensh blue dyeing ofoutstanding fastness to light and washng is obtained.

" EXAMPLE 15 By using 100 parts of the 10% dyestuif paste used inExample 7 instead of the dyestuff in Example 14, similarly good resultsare obtained.

EXAMPLE 16 Pigment process using a circulation-dyeing apparatus Ifsodium chloride and 2 parts by volume of acetic aicd of 40% strength areadded portionwise. The yarn is pigmented for 45 minutes while slowlyraising the temperature to 50 C. The pigment liquor is then completedexhausted. 10 parts by volume of sodium hydroxide solution of 30%strength and 3 parts of sodium hydrosulphite are then ,added and thepigmented yarn is vatted in the same bath for 30 minutes at 50 C.

The yarn is then rinsed, oxidised and finally soaped at the boil. Agreenish blue dyeing of good general fastness is obtained. 7.

" EXAMPLE 17 'Pad-roll process Cotton fabric is impregnated with apadding solution at 30 C. containing per 1000 parts of water, 100 partsof the 10% dyestuff paste used in Example 6, 50 parts.

of thiociethylene glycol, 50 parts of sodium hydroxide solution of 30%strength and 40 parts of sodium formaldehyde sulphoxylate.

The fabric is then passed through an infrared zone or steam channel sothat its temperature is raised to about 60 C. and then put into -aheated, preferably air-free, cabinet in whichthe rolled-up fabric isheated for 2-3 hours at 60 C. It is then oxidised and soaped in themanner described in Example 1. A greenish blue dyeing of good generalfastness is obtained.

EXAMPLE l8 a A printing paste prepared with the following in gredients:

100 parts of the 10% dyestuif paste used in Example 6, 150 parts ofwater, 50 parts of Rongalit and 700 parts of potassium carbonatethickener (total=l000 parts).

The potassium carbonate thickener is prepared from parts of wheatstarch, 90 parts of water, parts of glycerine, parts of British gumpowder, parts of tragacanth mucilage 60/1000. 170 partspof potassiumcarbonate and 240 parts of water (total: 1000 parts).

The paste is used to printing cotton fabric by means of a rouleauxprinting machine. The fabric is then dried and steamed for 5-8 minutesin a Mather-Flatt at 103 C. It is then after-treated in the usualmanner. A blue print of excellent fastness is obtained.

Similarly good results are obtained by using the above to print fabricsof viscose rayon and viscose staple rayon.

EXAMPLE 19 Two-phase printing process Cotton fabric is printed with theabove dye and thendried. The dry fabric is then padded with a solutioncontaining per 1000 parts of water, 120 parts of sodium hydroxidesolution of 30% strength, 70 parts of sodium hydrosulphite and 15 partsof borax.

The fabric is then immediately steamed or vatted at 120 C. without firstbeing dried. It is then oxidised and soaped in the manner described inExample 1. A greenish blue print of very good fastness to light andwashing is obtained.

When viscose staple rayon is printed in the above manner, similarly goodresults are obtained.

EXAMPLE 20 III IV 1 Blue.

1 Yellow.

' TABLE Contiriud ONa S OjONI g NH-OO- 1 Orange.

1 Yellow;

S 010 Na 7 S0;0Na

SOaO-Na TABLE-Continued I II III IV 14... 1 Yellow.

[Oi NHOC CONH (I? -COH1lT d b NH-OC-O-SOIONii ONa The dyestuifs shown inthe above table which has a solubility in water of -80 grams per literat 95 C., may be obtained, for example, by acylating the correspondingdyestuff intermediate that contains an acylatable amino group with acorresponding carboxylic acidsulfonic acid-dichloride with warming innitrobenzene, vatting the resulting dyestuif sulfochloride andreoxidiizng the dyestuff.

EXAMPLE 21 0.15 part of the dyestulf of the formula which is obtained byacylating the corresponding diamine with benzoic acid-para-sulfochloridein pyridine at 110 C. is used in the manner described in Example 1. Ared dyeing is obtained.

A dyestulf having similar color properties is obtained by acylating withdiphenyl-carboxylic acid-dichloride and sulfonating with dilute oleum.

EXAMPLE 22 The water-soluble dyestuif obtained by sulfonating4:4'-dibenzoyl-diamino-l l-dianthrimide carbazole with oleum containing10% of free 50;, at 50-60 C. which has a solubility in Water of about 50grams per liter at 90 C. is used in the following manner:

0.2 part of the dyestuff is dissolved in 50 parts of hot Water. Thissolution is then poured into a solution at 50 C. comprising 2 parts byvolume of a sodium hydroxide solution of strength and 1.2 part of sodiumhydrosulfite in 350 parts of water. 10 parts of cotton are addedimmediately and dyeing is carried out for 45 minutes at 50 C. with theaddition of 12 parts of sodium chloride. It is then oxidized, rinsed,acidified, thoroughly rinsed and finally hydrolyzed by boiling. Anolive-green dyeing of good fastness is obtained.

Similar dyeings may be obtained by using the dyestutf obtained byacylating 4:4-diamino 1:1 dianthrimidecarbazole with benzoic acid-metaor-para-sulfochloride in pyridine at 110 C., by sulfonating4:4'-di-(paraphenylbenzoylamino)-1: 1-dianthrimide-carbazole with oleumcontaining 5% of free S0 at room temperature, or by sulfonating 4:4dibenzoylamino-l:1'-dianthrimide with about 32% oleum at a raisedtemperature.

Another olive dyeing is obtained by using a dyestuff prepared bystirring 4:4'-diamino-1:1'-dianthrimide and benzoyl chloride withsulfuric acid of 100% strength and oleum of 63% strength at a raisedtemperature. The mixture is then cooled, a small amount of water isadded dropwise and then stirred for some time at 20-30 C. with group[and at least one sulfonic acid group bound] to the chromophone [throughits sulfur atom and] which is selected from those having at least 5condensed rings and those having at least 2 anthraquinone radicals.

2. A process as claimed in claim 1, wherein an anthraquinone vatdyestuft is used, which contains a sulfoaroylimino group bound throughits -CO--NH-- group in m-position of an anthraquinone nucleus.

3. A process as claimed in claim 2, wherein the quinone used contains aheterocyclic bridge between two anthraquinone radicals.

[4. A process as claimed in claim 1, wherein a polycyclic quinonesulfonic acid is used whose sodium salt is water soluble] 5. A processas claimed in claim 1, wherein the polycyclic quinone used contains ana-benzoyl-imino anthraquinone bond through an aromatic dicarboxylic acidbridge to a second anthraquinone radical.

6. A process as claimed in claim 3, wherein a triazinecontainingpolycyclic quinone is used.

7. A process as claimed in claim 1, wherein the reducing agent used isselected from the group consisting of an alkali-metal hydrosulfite,alkali-metal sulfide, alkalimetal hydrosulfide, thiourea dioxide andhydroxy alkanesulfonic acid.

8. A process for dyeing cotton according to claim 1.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

UNITED STATES PATENTS 3,110,541 11/1963 Weber et al 8-34 3,031,2524/1962 Stauble et a1. 834- 3,339,999 9/1967 Wick 834 DONALD LEVY,Primary Examiner

